JPH0354153A - Thermistor porcelain composition - Google Patents
Thermistor porcelain compositionInfo
- Publication number
- JPH0354153A JPH0354153A JP1187839A JP18783989A JPH0354153A JP H0354153 A JPH0354153 A JP H0354153A JP 1187839 A JP1187839 A JP 1187839A JP 18783989 A JP18783989 A JP 18783989A JP H0354153 A JPH0354153 A JP H0354153A
- Authority
- JP
- Japan
- Prior art keywords
- strength
- porcelain
- thermistor
- composition
- atomic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000000919 ceramic Substances 0.000 claims description 7
- 239000012071 phase Substances 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 229910052745 lead Inorganic materials 0.000 abstract 2
- 229910052596 spinel Inorganic materials 0.000 abstract 2
- 239000011029 spinel Substances 0.000 abstract 2
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、温度計測，温度補償などに用いられる負の温
度係数を有するサーミスタ磁器組戒物に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a thermistor porcelain assembly having a negative temperature coefficient used for temperature measurement, temperature compensation, etc.
従来の技術
近年、Ｍｎ．Ｎｉ，Ｚｒを主戒分とする酸化物系、いわ
ゆるスビネル系サーミスタ磁器は、軽薄１．２）
短小化の流れに沿ってチップ化が進み、セラミックエレ
メントに要求される項目も高精度のみならず、高強度で
あることが必要な条件になって来ている。BACKGROUND OF THE INVENTION In recent years, Mn. Oxide-based, so-called Subinel-based thermistor porcelain, which has Ni and Zr as its main components, is light and thin (1.2) With the trend of miniaturization, chipping is progressing, and the requirements for ceramic elements are not only high precision but also high precision. , high strength is becoming a necessary condition.
発明が解決しようとする課題
上記のようなＭｎ，ＮｉおよびＺｒを主成分とするスビ
ネル系サーミスタ磁器を用い、各種用途に展開する場合
、製品によって使用形態，方法は様々であるが、例えば
バネでセラミックエレメントを保持するタイプでのバネ
圧、円柱状セラミックエレメントの両端にキャップ状電
極を嵌合するタイプでの嵌め合い圧力、さらにはハンダ
付け時のヒートショックなど、セラミックエレメントに
かかる負荷には相当なものがあった。このため、セラミ
ック磁器の高強度が、工程における作業効率のみならず
、製品としての信頼性をも大きく左右するものでありな
がら、従来のスビネル系サーミスタ磁器は、高強度のも
のが必ずしも得られなく、適度に妥協しなければならな
いものであった。Problems to be Solved by the Invention When using Subinel-based thermistor porcelain whose main components are Mn, Ni, and Zr as described above, when it is used for various purposes, the form and method of use vary depending on the product. It is equivalent to the loads placed on the ceramic element, such as spring pressure in the type that holds the ceramic element, fitting pressure in the type that fits cap-shaped electrodes on both ends of the cylindrical ceramic element, and even heat shock during soldering. There was something. For this reason, although the high strength of ceramic porcelain greatly affects not only the work efficiency in the process but also the reliability of the product, it is not always possible to obtain high strength with conventional Subinel thermistor porcelain. , a reasonable compromise had to be made.
このようなことから、高強度のサーミスタ磁器を作るこ
とが望まれていた。For this reason, it has been desired to produce high-strength thermistor porcelain.
本発明はこのような問題点を解決するもので、磁器自身
の強度を強くすることによって、量産時における作業性
および製品としての信頼性を向上させることを目的とす
るものである。The present invention is intended to solve these problems, and aims to improve workability during mass production and reliability as a product by increasing the strength of the porcelain itself.
課題を解決するための手段
上記の課題を解決するために本発明のサーミスタ磁器組
成物は、金属元素としてＭｎ，ＮｉおよびＺｒを主戒分
とし、副成分としてｐｂ元素を０．１〜１０．０原子％
添加してなるものである。また、上記磁器組戒に、さら
にＢ，Ｓｉ元素の少なくとも一方を主戒分に対して０．
１〜１０．０原子％添加してなるものである。Means for Solving the Problems In order to solve the above problems, the thermistor ceramic composition of the present invention contains Mn, Ni, and Zr as the main metal elements, and PB element as a subcomponent of 0.1 to 10. 0 atomic%
It is made by adding. Furthermore, in the above-mentioned porcelain group precept, at least one of B and Si elements is added to the main precept at 0%.
It is added in an amount of 1 to 10.0 atomic %.
作用
さて、本発明にかかるサーミスタ磁器はスビネル構造を
もつ結晶であり、その焼結過程も一般に固相反応をとる
ことが知られている。そして、電気的な特性は結晶粒子
（半導体〉に起因するものであり、一方、磁器の強度は
破断面がアルミナ磁器と同じく粒界破壊であることから
、粒子そのものの強度に依存するものではなく、これよ
り弱い粒界の強度に起因していることが解る。また、こ
の両者は一応独立した事象と考えられる。Function The thermistor porcelain according to the present invention is a crystal having a Subinel structure, and it is known that the sintering process thereof generally takes a solid phase reaction. Electrical properties are due to crystal grains (semiconductors), while the strength of porcelain does not depend on the strength of the particles themselves, as the fracture surface is grain boundary fracture, just like alumina porcelain. It can be seen that this is due to the strength of the grain boundaries, which is weaker than this.Also, these two phenomena are considered to be independent phenomena.
そして、本発明の構戒によれば、Ｍｎ，ＮｉおよびＺｒ
を主成分とする組成に、Ｐｂを添加することにより、あ
るいはＢ，Ｓｉをさらに添加することによって、焼結時
点で部分的に液相反応が生じ、冷却時に主戒分元素のス
ビネル相を析出させ、その後、本発明の添加元素である
Ｐｂ．Ｂ，Ｓｉは粒界にとどまり、ガラス相を形威し、
強度の大幅増に寄与しているものとなる。これにより高
強度のサーミスタ磁器が得られることとなる。According to the structure of the present invention, Mn, Ni and Zr
By adding Pb or further adding B and Si to a composition whose main component is Pb, a liquid phase reaction occurs partially at the time of sintering, and the Subinel phase of the main precipitating element is precipitated during cooling. After that, Pb. B, Si remains at the grain boundaries and forms a glass phase,
This contributes to a significant increase in strength. As a result, high-strength thermistor porcelain can be obtained.
実施例 以下、本発明の実施例について説明する。Example Examples of the present invention will be described below.
まず、下記の第１表，第２表に示す組或となるように各
材料の秤量を行い、湿式ボールにて２０時間混合した後
に乾燥させ、その後、大気中で８００℃・２時間保持に
て仮焼処理を施した。この時、出発原料としては、市販
のＭｎ０２，Ｎｉ○，Ｚ ｒ０２．ＰｂＯ．Ｂ２０３．
Ｓ ｉｏ２を使用した。次に、仮焼処理を施したものを
再びボールミルにて湿式粉砕した後、乾燥させ、５％Ｐ
ＶＡ（ポリビニルアルコール）を１０ｗｔ％添加し、ラ
イカイ機にて顆粒を行い、１ ０ ０ ０ ｋｇ ／
ｃＪの加圧で４０ｍｍφ×２一の寸法に戒形を行った。First, each material was weighed to form the composition shown in Tables 1 and 2 below, mixed in a wet bowl for 20 hours, dried, and then held at 800°C for 2 hours in the air. A calcining treatment was performed. At this time, commercially available Mn02, Ni○, Zr02. PbO. B203.
Sio2 was used. Next, the calcined material was wet-pulverized again in a ball mill, dried, and 5% P
Add 10wt% of VA (polyvinyl alcohol) and granulate it using a Raikai machine to produce 1000 kg/
A shape of 40 mmφ x 2 mm was formed by applying a pressure of cJ.
次いで、この成形体を大気中、１２０℃で２時間保持し
て焼成し、電極は焼付銀電極を１５０℃にて両面に施し
た。Next, this molded body was held in the air at 120° C. for 2 hours and fired, and baked silver electrodes were applied to both sides at 150° C. as electrodes.
そして、電気的特性の測定は、オイル槽内にて２５℃に
て抵抗値（Ｒ２５）を測定し、比抵抗値（ρ）に換算し
、また５０℃の抵抗値（Ｒｓｏ）をさらに測定して、こ
の２点よりサーミスタ定数（Ｂ）を算出した。この算出
式は、Ｂ＝３８５４Ｘ Ｉ ｎ （Ｒ２Ｓ／Ｒｓｏ）を
用いた。さらに、磁器強度は焼結体をまず厚み０．５Ｍ
に研磨（＃８００）Ｌ、その後、ダイシングマシンにて
２５ｗｎＸ５＋ｎｍに切り出し、この試料を３点曲げ試
験法にて測定を行い、抗折強度を測定した。これらの測
定結果を下記の第１表，第２表に併せて示す。ここで、
測定値は試料数５ヶの平均値である。The electrical characteristics were measured by measuring the resistance value (R25) at 25°C in an oil bath, converting it to a specific resistance value (ρ), and further measuring the resistance value (Rso) at 50°C. The thermistor constant (B) was calculated from these two points. This calculation formula used B=3854X I n (R2S/Rso). Furthermore, the strength of the porcelain is determined by first making a sintered body with a thickness of 0.5M.
The sample was polished (#800) L, and then cut into 25wn x 5+nm pieces using a dicing machine, and this sample was measured using a three-point bending test method to measure the bending strength. These measurement results are also shown in Tables 1 and 2 below. here,
The measured value is the average value of 5 samples.
上記第１表，第２表に示す結果から明らかなように、本
発明実施例のサーミスタ組成によって、電気特性（比抵
抗値ρおよびサーミスタ定数Ｂ）を変化させずに磁器強
度を著しく高くずることができる。As is clear from the results shown in Tables 1 and 2 above, the thermistor composition of the embodiment of the present invention significantly increases the porcelain strength without changing the electrical characteristics (specific resistance value ρ and thermistor constant B). I can do it.
ここで、本発明において、ｐｂさらにはＢ．Ｓｉがそれ
ぞれ主成分に対して０．１原子％未満の場合には、磁器
強度を高くずるという本発明の効果が見られず、また一
方、１０．０原子％を超えた場合には比抵抗値ρが大き
く、かつサーミスタ定数Ｂは小さくなり、サーミスタ磁
器としての用をなさないものとなるため、請求範囲外と
している。Here, in the present invention, pb and B. When Si is less than 0.1 atomic % with respect to each main component, the effect of the present invention of increasing the porcelain strength is not observed, and on the other hand, when it exceeds 10.0 atomic %, the specific resistance is The value ρ is large and the thermistor constant B is small, making it useless as a thermistor porcelain, so it is outside the scope of the claims.
発明の効果
以上のように、本発明のサーミスタ磁器組成物によれば
、上記第１表，第２表に示すように電気特性を変化させ
ずに磁器強度を著しく高くすることができるものである
。したがって、この磁器を用いることにより、生産効率
が向上するのみならず、製品としての信頼性を飛躍的に
向上させることができるものである。また、磁器強度が
著しく向上したことにより、さらに薄く，小型の製品へ
の応用も可能となり、応答性の向上した′ｆ１２品への
展開も可能であるなど、本発明のサーミスタ磁器は画期
的な材料組成を提供することができるものである。Effects of the Invention As described above, according to the thermistor porcelain composition of the present invention, the strength of the porcelain can be significantly increased without changing the electrical properties, as shown in Tables 1 and 2 above. . Therefore, by using this porcelain, not only the production efficiency can be improved, but also the reliability of the product can be dramatically improved. In addition, the thermistor porcelain of the present invention is revolutionary, as the strength of the porcelain has been significantly improved, making it possible to apply it to even thinner and smaller products, and to develop 'f12 products with improved response. It is possible to provide a material composition with a wide range of properties.
Claims (2)
し、副成分としてＰｂ元素を０．１〜１０．０原子％添
加したことを特徴とするサーミスタ磁器組成物。(1) A thermistor ceramic composition characterized in that the main components are Mn, Ni, and Zr as metal elements, and 0.1 to 10.0 atomic % of Pb element is added as a subcomponent.
の少なくとも一方を主成分に対して０．１〜１０．０原
子％添加したことを特徴とするサーミスタ磁器組成物。(2) A thermistor porcelain composition characterized in that 0.1 to 10.0 atomic % of at least one of B and Si elements is added to the porcelain composition according to claim 1, based on the main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1187839A JP2715573B2 (en) | 1989-07-20 | 1989-07-20 | Thermistor porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1187839A JP2715573B2 (en) | 1989-07-20 | 1989-07-20 | Thermistor porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0354153A true JPH0354153A (en) | 1991-03-08 |
| JP2715573B2 JP2715573B2 (en) | 1998-02-18 |
Family
ID=16213134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1187839A Expired - Fee Related JP2715573B2 (en) | 1989-07-20 | 1989-07-20 | Thermistor porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2715573B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285789A (en) * | 2011-05-31 | 2011-12-21 | 中国科学院新疆理化技术研究所 | Pb-containing four-component system thermosensitive resistor with negative temperature coefficient |
| RU2767488C1 (en) * | 2020-12-28 | 2022-03-17 | Федеральное государственное бюджетное образовательное учреждение высшего образования «МИРЭА - Российский технологический университет» | Thermistor material |
-
1989
- 1989-07-20 JP JP1187839A patent/JP2715573B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285789A (en) * | 2011-05-31 | 2011-12-21 | 中国科学院新疆理化技术研究所 | Pb-containing four-component system thermosensitive resistor with negative temperature coefficient |
| RU2767488C1 (en) * | 2020-12-28 | 2022-03-17 | Федеральное государственное бюджетное образовательное учреждение высшего образования «МИРЭА - Российский технологический университет» | Thermistor material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2715573B2 (en) | 1998-02-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |